Use of organorhenium compounds for the oxidation of multiple C--C-bonds, oxidation processes based theron and novel organorhenium compounds

ABSTRACT

Compounds of the formula 
     
         (R.sup.11 Re).sub.k O.sub.1 R.sup.12 .sub.m ·L.sub.n (III) 
    
     in which 
     R 11  is a hydrocarbon group which is bonded to the rhenium via a carbon atom to which at least one hydrogen atom is still attached, 
     R 12  is aliphatic hydrocarbon radical which may contain silicon bridge atoms, or is an unsubstituted or substituted phenyl radical, 
     L is a ligand which is bonded to the rhenium metal via one to three oxygen and/or nitrogen atoms, and the 
     index k is 1 or 2, the index 1 is an integer from 1 to three times k, the index m is zero or an integer from 1 to twice k, and the index n is an integer from 1 to three times k, and in which the indices k, l, m and n are selected such that their combination satisfies the 5-, 6- or 7-valence of rhenium. 
     The invention also provides compounds of the formula 
     
         (polymer).sub.f ·(CH.sub.3 ReO.sub.3).sub.8       (VI) 
    
     in which the rhenium compound CH 3  ReO 3  is bonded to the polymer via amine or amide nitrogen in the polymer. It further provides for the use of compounds of the formula R 1   a  Re b  O c  (I) in which a is 1 to 6, b is 1 to 4 and c is 1 to 14 and the total of a, b and c is such that the 5-valence to 7-valence of rhenium is satisfied, with the proviso that c is not greater than three times b, and in which R 1  represents an optionally fluorinated hydrocarbon, or of compounds of the formula (R 11  Re) k  O l  R 12   m  ·L n  (III) or (polymer) f  ·(CH 3  ReO 3 ) g  (VI), as catalysts for the oxidation of multiple C--C bonds and also provides processes of this type.

DESCRIPTION

The use of organorhenium compounds for the oxidation of multiple C--C-bonds, oxidation processes based thereon and novel organorhenium compounds

The invention relates to the use of certain organorhenium compounds for the oxidation of multiple C--C bonds, oxidation processes based thereon, in particular for the preparation of epoxides and optionally diols by oxidation of olefinic compounds and for the preparation of diketones or α,β-olefinically unsaturated monoketones by oxidation of alkynes, in each case with hydrogen peroxide using organorhenium compounds, and to novel organorhenium compounds.

It is known that metal oxides act selectively as oxidizing agents for unsaturated organic compounds of different categories. For instance, the binary oxides M_(x) O₆ of the metals (M) vanadium (V₂ O₅), molybdenum (MoO₃) and osmium (OsO₄) in particular are used in practice, for example as catalysts for converting olefins into epoxides. In these reactions, 1,2-diol derivatives can also be produced, and in the case of OsO₄, the cis-glycols can be produced stereospecifically. These metal oxides are often not used as stoichiometric reagents but in the presence of hydrogen peroxide, tert-butyl hydroperoxide, m-chloroperbenzoic acid and so on in only catalytic amounts. Although the reaction mechanisms are not known in detail, the action of catalyst systems of this type (for example metal oxide/H₂ O₂) is ascribed to hydroperoxo-metal completes as the actually effective catalyst species (structural unit M--O--OH).

The catalyst system OsO₄ /H₂ O₂ has particular importance for the selective oxidation of olefins to form cis-1,2-diols. In this case, catalytic amounts of osmium tetroxide are sufficient. A particularly well known reagent is Milas' reagent: H₂ O₂ /tert-butanol/OsO₄ (N. A. Milas and S. Sussaman, J. Am. Chem. Soc. 58 (1936) 1,302-04 and N. A. Milas and S. Sussaman J. Am. Chem. Soc. 59 (1937) 2,345-47).

However, in this connection, the abovementioned metal oxides also have disadvantages, in particular high cost (osmium), high toxicity (osmium), lack of selectivity for the formation of epoxides and cis-1,2-diols from the olefinic precursors (chromium, molybdenum, tungsten) and the short life of the catalyst under the given reaction conditions (in particular, OsO₄ /H₂ O₂ /tert-butanol).

The object is therefore to provide a simple-to-handle, storable, non-toxic and effective catalyst system which ideally is easily accessible and which achieves the desired selectivity in the oxidation of olefins and certain alkynes. 1,2-Diols and epoxides are of great interest for further industrial processing and so are 1,2-diketones and α,β-olefinically unsaturated monoketones.

The obvious idea of using, instead of the oxidation catalysts known from the literature, oxides of the element rhenium which is adjacent to osmium and molybdenum in the periodic table and which is many times cheaper than osmium, these oxides having the formula Re_(x) O_(y), has not been verifiable in practice. For instance, the oxides Re₂ O₇, ReO₃ and Re₂ O₅, in the presence or absence of other oxidizing agents such as hydrogen peroxide and tert-butyl hydroperoxide, are either inactive or unselective in the oxidation of olefins. Only two very similar reports appear in the literature concerning the use of rhenium compounds, in particular rhenium oxides, rhenium halides and perrhenates, as catalysts for oxidation with oxygen at -50° to +125° C. (U.S. Pat. No. 3,316,279) and with hydrogen peroxide at 100°-150° C. (U.S. Pat. No. 3,518,285). In both cases, mixtures of epoxides and ketones were obtained. The oxidation with oxygen according to U.S. Pat. No. 3,316,279 can also employ "oxidation modifiers", namely nitrogenous compounds, in particular organic cyanides, pyridines and quinolines which are intended to halt the reaction to a certain extent at the epoxide stage and to suppress rearrangements; if they are left out, consequent reactions occur such as the formation of condensation products (by dimerization of the epoxides to form substituted dioxanes or polymerization to form polyethers) and the formation of α-hydroxycarbonyl compounds by further oxidation of the epoxides. Moreover, the process according to U.S. Pat. No. 3,316,279 is intended to be carried out at pressures from 1 to about 250 atmospheres, i.e. operation at elevated pressure is virtually obligatory, as can also be seen from the examples. However, reactions under elevated pressure require increased expenditure on plant.

Applicant's own attempts to use the abovementioned rhenium oxides, for example Re₂ O₇ and ReO₃, as catalysts for olefin oxidation were likewise unsuccessful. Similarly, Na[ReO₄ ], NH₄ [ReO₄ ] and [N(n-C₄ H₉)₄ ][ReO₄ ] proved ineffective, as did organometallic mixed compounds such as the monomeric derivative (trimethylstannoxy)rheniumtrioxide of the formula [(CH₃)₃ SnO]ReO₃ described by W. A. Herrmann et al.(W. A. Hermann, J. G. Kuchler, J. K. Felixberger, E. Herdtweck and W. Wagner, Angew. Chem. 100 (1988) 420-422) and the compounds [(CH₃)₃ SiO]ReO₃ (M. Schmidt and H. Schmidbaur, Chem. Ber. 92 (1959) 2,667-2,669) and [(C₆ H₅)₃ SiO]ReO₃ (H. Schmidbaur and D. Koth, Chem. Zeitung 100 (1976) 290-291).

It is known from the paper by W. A. Herrmann et al., loc. cit., that of the true organometallic compounds of rhenium, methylrhenium trioxide CH₃ ReO₃ in the presence of AlCl₃ and tetramethyltin brings about the metathesis of open-chain olefins and also the catalytic ring-opening polymerization of cycloolefins to form polyalkenamers. The same paper discloses that methylrhenium oxide is methylated by treatment with dimethylzinc to form a sublimable, lemon-yellow methylrhenium oxide of the formula (CH₃)₄ Re₂ O₄, i.e. a compound containing 6-valent rhenium. This compound too, in the presence of tetramethyltin and aluminum chloride, catalyzes the metathetic ring-opening polymerization of cyclopentene.

Finally, the above paper discloses that (CH₃)₄ Re₂ O₄ is converted by further methylation with dimethylzinc to (CH₃)₆ Re₂ O₃, i.e. likewise to a compound containing 6-valent rhenium. According to said paper, this compound is capable of catalyzing the ring-opening polymerization of cyclopentene even in the presence only of AlCl₃, i.e. without the presence of the cocatalyst Sn(CH₃)₄ which is necessary in other cases.

It was certainly not possible to conclude from this and the other references that organorhenium compounds also act as catalysts for the completely different reaction of the oxidation of multiple C--C bonds, particularly in the absence of a cocatalyst.

Surprisingly, it has now been found that certain organic compounds of rhenium are suitable as highly active catalysts for the oxidation of multiple C--C bonds, in particular for the selective conversion of olefins into 1,2-diols or epoxides, if the said compounds are used with hydrogen peroxide in a liquid medium.

The present invention accordingly provides for the use of compounds of the general formula R¹ _(a) Re_(b) O_(c) (I) in which a is 1 to 6, b is 1 to 4 and c is 1 to 14 and the total of a, b and c is such that the 5-valence to 7-valence of rhenium is satisfied, with the proviso that c is not greater than three times b, and in which the R¹ moieties are identical or different and represent a non-aromatic hydrocarbon radical having 1 to 10 carbon atoms or aralkyl having 7 to 9 carbon atoms and R¹ may be at least partially fluorinated, and the compounds do not contain more than three groups having more than 6 carbon atoms per rhenium atom and the carbon atom in the α-position still has attached to it at least one hydrogen atom, and for the use of novel compounds of the formula (R¹¹ Re)_(k) O_(l) R¹² _(m).L_(n) (III) in which R¹¹, R¹², L, k, l, m and n have the meaning given below, and also for the use of novel compounds of the formula (polymer)_(f).(CH₃ ReO₃)_(g) (VI), in which the rhenium compound CH₃ ReO₃ is bonded via amine nitrogen or amide nitrogen to the polymer and in which the quotient g/f expresses the ratio by weight of the two components and is in the range between 0.01 and 0.2, preferably between 0.02 and 0.1, as catalysts for the oxidation of multiple C--C bonds.

The invention also provides compounds of the formula (R¹¹ Re)_(k) O_(l) R¹² _(m).L_(n) (III) in which

R¹¹ is a non-aromatic hydrocarbon radical having 1 to 10 carbon atoms or aralkyl having 7-9 carbon atoms which in each case is bonded to the rhenium via a carbon atom to which at least one hydrogen atom is still attached, and advantageously these are alkyl radicals having 1 to 9 carbon atoms and cycloalkyl having 5 to 10 carbon atoms,

R¹² is a linear or branched aliphatic hydrocarbon radical having 1 to 10 carbon atoms, which may also contain up to 3 silicon bridge atoms, or a phenyl radical which is unsubstituted or contains up to 3 substituents from the group comprising alkyl and/or alkoxy jointly having at most 6 carbon atoms or contains up to five fluorine atoms,

L is a ligand which is bonded via one to three oxygen atoms and/or nitrogen atoms to rhenium and the index k is 1 or 2, the index l is an integer from 1 to three times k, the index m is zero or an integer from 1 to twice k and the index n is an integer from 1 to three times k.

The indices k, l, m and n must be selected such that their combination satisfies the 5-, 6- or 7-valence of rhenium; the ligand L may be 1-, 2- or 3-dentate and may itself be neutral or anionic.

In the formulae I and III, R¹ and R¹¹ are a non-aromatic hydrocarbon radical having 1 to 10 carbon atoms or aralkyl having 7 to 9 carbon atoms, such as benzyl, which in each case is bonded to the rhenium via a carbon atom to which at least one hydrogen atom is still attached, in particular alkyl radicals having 1 to 10 carbon atoms or cycloalkyl having 5 to 10 carbon atoms. Suitable alkyl radicals are methyl, ethyl, propyl, isopropyl and the various butyl, pentyl, hexyl or octyl radicals, such as ethylhexyl, and decyl radicals; other suitable radicals are cycloalkyl radicals such as cyclopentyl, cyclohexyl, alkylated cyclohexyl such as hydrogenated toluyl, xylyl, ethylphenyl, cumyl or cymyl, and 1-norbornyl. Particular preference is given to methyl.

The terms alkyl and cycloalkyl naturally imply that the groups contain no multiple bonds. R¹ may be at least partially fluorinated. However, for steric reasons it is inadvisable to have more than three groups of more than six carbon atoms per rhenium atom in compounds I and III; advantageously, the compounds contain only at most one group of this type.

The invention also provides the abovementioned compounds of the formula (polymer)_(f).(CH₃ ReO₃)_(g) (VI).

The invention also provides a process for the preparation of epoxides by oxidation of olefinic compounds with hydrogen peroxide in the presence of catalysts, and a further, optional reaction to form diols, which comprises oxidizing olefins of the formula YCZ═CZ--(CX₂)_(n) R² (II) in which R², X, Y, Z and n have the meanings given below at a temperature of -30° to +80° C., preferably of 0° to 40° C., in a liquid medium in the presence of rhenium compounds of the abovementioned formula R¹ _(a) Re_(b) O_(c) (I) in which R¹ , a, b and c have the meanings given above, or in the presence of compounds of the formula (Re¹¹ Re)_(k) O_(l) R¹² _(m).L_(n) (III) as claimed in claim 1 or in the presence of compounds of the formula (polymer)_(f).(CH₃ ReO₃)_(g) (VI), as previously defined, and

a) isolating the epoxides obtained or

b) converting the epoxides obtained in the presence of the same catalysts into 1,2-diols or

c) converting the epoxides obtained in the customary manner with bases into 1,2-trans-diols or

d) converting the epoxides obtained in the customary manner with acids into cis-trans mixtures of 1,2-diols.

In the formula II, n represents 0 or an integer from 1 to 28; X is H or F; Y is H, alkyl or a mono-olefinically unsaturated or poly-olefinically unsaturated, unbranched or branched, open-chain or cyclic hydrocarbon radical having 2 to 28 carbon atoms, for example alkyl having 1 to 10 carbon atoms or aryl having 6 to 10 carbon atoms, or COOR³. Z represents H or an aromatic or non-aromatic hydrocarbon radical having 1 to 6 carbon atoms, which may be cyclic, for example cyclohexyl, but is preferably an open-chain alkyl having 1 to 4 carbon atoms. The two symbols Z may also simultaneously represent CO groups which are bonded in the o-position to a benzene radical, as in naphthoquinone, or may form a cycloaliphatic ring together with C═C as in cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclooctatetraene, cyclododecene, cyclohexadecadiene or limonene. The substituents Z may be identical or different. R² is H, halogen, an acyclic hydrocarbon radical without triple bonds having up to 24 carbon atoms, which may contain up to 5 double bonds, as in squalene, aryl having up to 10 carbon atoms and which may contain 1 to 3 substituents on the ring which are insensitive to the oxidation conditions used, ω-oxoalkenyl, COOR³ or OR⁴, where R³ is alkyl or aryl and R⁴ is alkyl, aryl or trialkylsilyl R⁵ ₃ Si. The alkyl groups in R⁵ contain 1 to 5, preferably 1 to 3, carbon atoms. In R³ and R⁴, alkyl in each case represents those with 1 to 15, preferably 1 to 6, carbon atoms and aryl represents phenyl which may contain a further one to three substituents on the ring which are inert under the oxidation conditions used, such as halogen, for example fluorine, chlorine or bromine, NO₂, OR⁶ and/or alkyl. The radicals R⁶ are identical or different and may be hydrogen or alkyl having 1 to 4 carbon atoms. (CX₂)_(n) and R² jointly have at most 28 carbon atoms. Y, (CX₂)_(n) and R² may also form a cycloaliphatic ring system together with the group CZ═CZ which may contain up to 5, preferably up to 3 olefinic bonds or up to two carbonyl groups. Ring systems of this type are present for example in pinene and dipentene (limonene).

Halogen R² may be fluorine, chlorine, bromine or iodine. If Z is hydrogen and R² is halogen, the latter is preferably bromine. Compounds in which at least one X=F are for example 4-(perfluoro-n-hexyl)-1-butene of the formula (n-C₆ F₁₃)--CH₂ --CH₂ --CH═CH₂ and perfluoropropene C₃ F₆. The number of chain units n varies preferably in the range from 1 to 12 and in particular up to 8.

The invention also provides a process for the oxidation of the formula R⁷ C═C═CR⁸ (IV) and of alkynes of the formula R⁹ C═CR¹⁰ (V) in which R⁷ to R¹⁰ are in each case alkyl having 1 to 4 carbon atoms or aryl containing 1 or 2 aryl nuclei such as naphthyl, biphenyl or in particular phenyl and the aryl may in each case be identical or different and may have other substituents which for their part are insensitive under the oxidation conditions used. This process converts cumulenes into hydroxy compounds whose hydroxyl group is located at the carbon atom with the least number of hydrogen atoms, and alkynes into 1,2-diketones or, if at least one of the radicals R⁹ and R¹⁰ is bonded to the acetylenic group by a CH-group, into α,β-olefinically unsaturated monoketones. These oxiations are likewise carried out using rhenium compounds of the formulae I, III and VI as defined above with hydrogen peroxide at a temperature of -30° to +80° C., preferably of 0°-40° C., in a liquid medium.

According to another embodiment of the invention, it is also possible to oxidize compounds of the formula R¹³ HC═CHR¹⁴ (VII) in which R¹³ represents aryl with up to 10 carbon atoms and R¹⁴ represents H, CH₃ or aryl having up to 10 carbon atoms and in which the aryl radicals are identical or different with hydrogen peroxide at a temperature of -30° to +80° C., preferably of 0°-40° C., in a liquid medium in the presence of rhenium compounds of the formulae I, III or VI as defined above. This arrangement produces predominantly aldehydes. Suitable starting materials for this embodiment of the invention are for example styrene, the various vinyltoluenes and stilbene. Here, too, the aryl may have other substituents which are insensitive under the oxidation conditions used, as for example in 2,3,4,5,6-pentafluorostyrene.

The compounds of the formula I are partly known (W. A. Herrmann et al. Angew. Chem. 100 (1988) 420-422) and partly the subject of earlier European Patent Application P 89 122 437.0; however, their suitability as oxidation catalysts is novel and was not foreseeable. On the contrary, they are the first organometallic compounds of rhenium which it is possible to use successfully for carrying out oxidation processes. By virtue of their solubility properties, they are particularly suitable as homogeneous catalysts. They also have the particular advantage that they can readily be synthesized from commercially available Re₂ O₇ with the aid of commercially available substances which bring about the transfer of organic groups, for example in the case of R¹ ═CH₃ by reaction with commercially available tetramethyltin or commercially available dimethylzinc. Said compounds are insensitive to air and moisture, water and acid, have a long shelf life at room temperature and are highly active catalysts in combination with hydrogen peroxide, inorganic peroxides such as alkali metal peroxides, in particular sodium peroxide, and also percarboxylic acids and their salts such as m-chloroperbenzoic acid, peracetic acid and magnesium monoperoxophthalate, for oxidations according to the invention.

The compounds of the formula III differ from those of the formula R¹ _(a) Re_(b) O_(c) (I) essentially in that they additionally contain nitrogenous bases and/or oxide oxygen or oxo oxygen or hydroxyl which are complexed with the rhenium. In the radical R¹², alkyl can be, for example, methyl, ethyl, propyl, or one of the butyl, pentyl, hexyl, octyl or decyl radicals. Examples of substituted phenyl radicals are the tolyl, xylyl and anisyl radicals.

The ligand is, for example, an amine such as ammonia, a primary amine H₂ NR, a secondary amine HNR₂ or a tertiary amine NR₃ in which R can be a branched or unbranched alkyl having 1-18 carbon atoms, an aliphatic azacycle such as quinuclidine, an aromatic azacycle such as pyridine and its ring-substituted and fused derivatives such as 8-hydroxyquinoline, a O,I'-, N,O- or N,N'-chelate ligand such as 2,2'-bipyridine, 2-aminopyridine, 2-(aminomethyl)pyridine, a substituted piperazine, an aminosubstituted piperidine or pyrrolidine, a methoxy-substituted pyridine such as 2-methoxypyridine, a 1,3-diketone such as acetylacetone, a 1,2-diketone such as diacetyl or pentane-2,3-dione, a β-aminoalcohol such as 2-aminoethanol, 2-aminophenol, 2-amino-1-butanol and ephedrine, a β-aminoaldehyde, a β-aminoketone, a 1,2-diimide, a β-aminoether such as 2-(aminomethyl)tetrahydrofuran, an aromatic N-oxide such as 2,2'-bipyridine-N,N-dioxide and pyridine-N-oxide, a 1,2-diamine such as ethylenediamine or a hydroxycarboxylic acid such as tartaric acid and its esters.

The ligand L coordinated to the rhenium atom may also be bonded to other metals by coordinate bonds, for example in CH₃ ReO₃.[(NH₂ C₆ H₅)Cr(CO)₃ ], CH₃ ReO₃.[(NC₄ H₄)Mn(CO)₃ [ and CH₃ ReO₃.[aminoferrocene].

The compounds of the formula III can be obtained simply by reacting the precursor R¹¹ ReO₃, for example CH₃ ReO₃, in an organic solvent, for example methylene chloride, diethyl ether, tetrahydrofuran or toluene, with the corresponding ligands L at room temperature and then evaporating the solution to dryness under reduced pressure or isolating the adduct by crystallization. If desired, the product can be purified by distillation, by recrystallization or by sublimation under reduced pressure. As a rule, the resulting substances are stable to air, heat and water.

Suitable liquid media for carrying out the oxidation reactions are organic solvents, for example tetrahydrofuran, monhydric alcohols having 1 to 5 carbon atoms such as methanol, ethanol, the various propanols and butanols, and aromatic hydrocarbons such as toluene and the various xylenes. Another suitable liquid medium is a two-phase system of water on the one hand and water-immiscible organic solvents on the other hand, in which the hydrogen peroxide is dissolved. A solution of hydrogen peroxide in tert-butanol is particularly suitable.

In the simplest form of the invention for operation and use, the procedure is as follows:

a) A catalyst solution is prepared which contains about 10-30 mg of CH₃ ReO₃. If tert-butanol is used for preparing this solution, the solution is a deep yellow color and has a shelf life of several weeks at -30° C., for example in a freezer chest, without diminution of the activity. This is a particular advantage of the catalysts according to the invention. The solution therefore does not need to be freshly prepared for each batch. It is possible to increase the batch sizes many times over without incurring any disadvantages.

b) The solution prepared in a) is added with stirring to the hydrocarbon to be oxidized, which is optionally dissolved in a non-oxidizable organic solvent, in such a way that the highly exothermic oxidation reaction does not cause the mixture to boil. There are then various possibilities for carrying out the reaction. It is advantageous to work in the temperature range from 0° C. (ice cooling) to 50° C. However, it is also possible to work at lower temperatures. If relatively low temperatures are employed, for example -30° to +10° C., although the reaction runs more and more slowly with progressively lower temperatures, the oxidation of the olefins leads more and more selectively to the epoxide, and further reaction to form the diol is suppressed at progressively lower temperatures. If the intention from the start is to form 1,2-diols, it is recommended to work at temperatures above 10° C. in the given range. The formation of 1,2-diols is favored in that the oxidation is highly exothermic, and the higher the starting temperature the more the reaction medium is heated and consequently the faster the reaction proceeds.

Both in the oxidation of the olefins and of the cumulenes and alkynes, the reaction medium advantageously contains 1 to 30% by weight of H₂ O₂. If special safety precautions are taken, it is also possible to use solutions in which the proportion of H₂ O₂ is higher. Advantageously, the solution should not contain any water, although the presence of water is not harmful, since water is formed in the stoichiometric amount from the hydrogen peroxide during the reaction.

c) If an excess of peroxide is present, this can be destroyed catalytically by adding MnO₂. The batch is then worked up by customary methods, for example by distillation. The catalyst CH₃ ReO₃ can be recovered (proved using a combination of gas chromatography, mass spectrometry and infrared spectroscopy).

The catalysts used according to the invention have a high efficiency. Generally, the catalyst is present in the reaction medium in an amount from 0.01 to 7% by weight, preferably from 0.03 to 1.0% by weight. However, in particular cases, it is also possible to use it in greater or lesser concentrations. There is virtually no consumption of the catalyst during the reaction, as befits the use of the term catalyst. It is easily possible to oxidize for example a ten thousand fold molar amount of olefin with the catalyst before regeneration is necessary. The rate of oxidation naturally also depends on the reaction temperature.

If olefins of the formula II are oxidized with the aid of the catalyst proposed according to the invention, then in the temperature range from -30° to +40° C. these olefins are initially converted selectively into the corresponding epoxides, as has been shown from a kinetic study using cyclohexene and also trans-4-octene as examples. The greater the temperature constancy, the better the selectivity in many cases. The degree of conversion is also influenced very favorably by maintaining the temperature constant. The optimal conditions in individual cases are often governed also by the structure of the alkene or alkyne which is to be oxidized. It is possible for the initially formed epoxides to be converted in a subsequent reaction into the corresponding 1,2-diols. In the case of the OsO₄ -catalyzed olefin oxidations according to Milas et al., loc. cit., except with allylalcohols, the 1,2-diols and subsequent oxidation products such as ketols are always produced, but not epoxides.

In a further embodiment of the invention, the catalyst CH₃ ReO₃ can also be used in the form in which it is taken up (immobilized) on a polymer which contains amine or amide nitrogen. Generally in this case, a compound (polymer)_(f).(CH₃ ReO₃)_(g) (VI) is formed in which the rhenium compound is bonded via amine nitrogen or amide nitrogen and in which the quotient g/f gives the ratio by weight of the two components and is in the range of between 0.01 and 0.2, preferably between 0.02 and 0.1. The polymers which are to be used therefore have nitrogen-containing groups at their surface, and the nitrogen atom may be present not only in aromatic groups but also in aliphatic groups and moreover in amide groups (an example is poly(4-vinylpyridine) which is marketed under the name Reillex--cf. Aldrich Catalog No. 22,696-3). In this embodiment, the polymer substance need not serve as a substrate only but can, if suitable substituents are selected, also act as a reaction-controlling component (promotor). The degree of coating of the substrate can moreover be used to control the reaction rate, the conversion and the selectivity of the oxidation. The great advantage of the compounds VI is furthermore that the catalyst can readily be separated off again after the reaction has ended, for example by simple filtration, and regenerated, and the activity and also the conversion and selectivity are only slightly reduced, if at all, in subsequent reaction batches.

In an advantageous embodiment, it is also possible to proceed by using a dissolved catalyst of the formula I in which R¹ is CH₃ and, having used this catalyst, removing it from the solution by reacting it with a polymer which contains amine or amide nitrogen and obtaining the catalyst either as a compound of the formula VI or regenerating it from this form by treatment in high vacuum at a temperature of at least 200° C. as a compound of the formula I in which R¹ is CH₃.

In the characterizations of individual substances in the following examples, the abbreviations have the following meanings: s singlet, d doublet, t triplet, q quartet, sept septet, m multiplet, br broad signal shape, sst very strong, st strong and EI-MS electron impact mass spectrum.

The starting materials for the following examples were prepared as follows:

(A) Preparation of methylrhenium trioxide CH₃ ReO₃

The synthesis of CH₃ ReO₃ from Re₂ O₇ and Sn(CH₃)₄ is only successful if it is carried out with the rigorous exclusion of moisture. For this reason, well dried solvents are required. Advantageously, the reaction vessel (for example Schlenk tube) is kept for some time before use at 400°-600° C. under high vacuum and the Re₂ O₇ is subsequently weighed in.

10.00 g (20.64 mmol) of dirhenium heptoxide Re₂ O₇ (76.8% by weight of Re) were dissolved in 90 ml of anhydrous tetrahydrofuran. Meanwhile, the solvent was rapidly added with vigorous stirring, for example using a magnetic stirrer, in order to avoid agglomeration of Re₂ O₇. To the solution obtained in this way, which can have a slightly brownish color, 3.15 ml (22.71 mmol; 1.1-fold excess) of commercially available tetramethylstannane Sn(CH₃)₄ were added. Since this reagent is toxic, all operations must be carried out with suitable safety precautions, for example under powerful fume extraction. The reaction mixture was then boiled under reflux for 4 hours. Longer reaction times had no adverse effect on the reaction. After cooling the solution to room temperature, the solvent was slowly removed under oil pump vacuum until the residue had a paste-like consistency. Significant amounts of CH₃ ReO₃ can then sublimate off. For this reason, further removal of the solvent was only carried out after the apparatus had been provided with a cold finger condenser cooled to between -10° C. and 0° C. (circulating cryostat).

After the solvent had been completely removed, the product was isolated in the form of colorless needles at about 80° C. in the said vacuum by sublimation onto the cooled sublimation finger condenser. The yield of analytically pure substance was 4.85 g (94% of theory, according to the reaction equation Re₂ O₇ +Sn(CH₃)₄ →CH₃ ReO₃ +[(CH₃)₃ SnO]ReO₃).

The gray residue was taken up in 40 ml of tetrahydrofuran. The solution was filtered through a layer of Al₂ O₃ approximately 2 cm in depth. From the colorless filtrate, by removal of the solvent, it was possible to isolate the compound [(CH₃)₃ SnO]ReO₃ as an analytically pure colorless powder; the yield was 8.12 g (95% of theory based on the equation given above).

Data for methylrhenium trioxide

Melting point 106° C.--IR (cm⁻¹, KBr): 1,002 sst, 950 sst, br[v(Re═O)]. --¹ H-NMR (CDCl₃, 28° C.): δ(CH₃)=2.61 s. --¹³ C-NMR (CDCl₃, 28° C.): δ(CH₃)=19.03 [¹ J(C,H)=138 Hz]. --¹⁷ O-NMR (CDCl₃, 28° C.): δ(O) =829 ppm. --EI-MS: m/z=248/250 (molecule-ion, with the appropriate isotopes present ¹⁸⁵ Re/¹⁸⁷ Re). The substance can be kept at room temperature without decomposition.

CH₃ ReO₃ : calc.: C 4.82, H 1.20, O 19.26, Re 74.72; (249.21): found: C 4.84, H 1.19, O 19.30, Re 74.78.

(B) Preparation of the catalyst solution

25 ml of 30% strength H₂ O₂ (of analytical quality) were added to 100 ml of tert-butanol and stirred for one hour with 30 g of anhydrous MgSO₄. The magnesium sulfate was then filtered off. The oxidation solution obtained was carefully kept under an atmosphere of nitrogen. To 2.68 ml of this solution, 20 mg of solid methylrhenium trioxide were added. The solution, consisting of the catalyst CH₃ ReO₃ (30 mmol/liter) and the oxidizing agent H₂ O₂ became instantly yellow. The solution can be kept at 0° C. for a relatively long time and retains its activity at this temperature and at even lower temperatures. The amount of catalyst can be reduced to 3 mmol/liter, but then, for the same conversion, the oxidation reaction takes longer.

EXAMPLES Examples 1-35 Oxidation of alkenes, cumulenes and alkynes

The relevant alkene or alkyne (cf. Table 1) was added to the catalyst solution prepared according to B, and there was a pronounced increase in the temperature of the batch, sometimes up to the boiling point. The amount of alkene and cumulene used, based on the number of double bonds, corresponded to the molar amount of H₂ O₂ which was present. In the oxidation of alkynes, twice the amount of H₂ O₂ was used per triple bond. After 5 to 30 minutes, the solution had again become colorless and the reaction had come to a stop, i.e. the equilibrium reached did not alter even after a relatively long time.

The excess H₂ O₂ remaining in the solution was removed by dissolving the entire batch in 10 ml of tetrahydrofuran and adding 1 g of manganese dioxide MnO₂ , i.e. an excess, to destroy the peroxide. After 10 min, the evolution of gas had ended. The suspension was filtered through a glass sinter filled with ®Celite (registered trade mark of Manville Corp., Denver, U.S.A.) and subsequently washed three times with tetrahydrofuran. The solvent was removed from the filtrate under reduced pressure. The crude product thus obtained was analytically pure after washing three times with 20 ml of n-hexane in each case. If necessary, the product was worked up by distillation or recrystallization, optionally at reduced temperature.

The use of an excess of H₂ O₂ allows the yield to be significantly improved in many cases.

                                      TABLE 1                                      __________________________________________________________________________     for Oxidation reactions                                                                      Reaction                                                         Example                                                                             Starting Material                                                                       conditions*                                                                            Products   Yield                                         __________________________________________________________________________      1   Propylene                                                                               -10° C.,                                                                     12 h                                                                              Propyleneoxide                                                                             50%**                                                              1,2-Propanediol                                                                           50%                                            2   2-Butylene                                                                              -10° C.,                                                                     10 h                                                                              2,3-Butanediol                                                                             100%**                                        3   1-Pentene                                                                               RT,  1 h                                                                               1,2-Epoxypentane                                                                          55%                                            4   cis-2-Pentene                                                                           RT,  3 h                                                                               Pentane-2,3-diol                                                                          10%                                                                 2,3-Epoxypentane                                                                          90%                                            5   2-Methyl-1-                                                                             RT,  4 h                                                                               Epoxy-2-methyl-                                                                           65%                                                butene           butane                                                    6   2,3-Dimethyl-                                                                           RT,  1 h                                                                               2,3-Dimethyl-                                                                             75%                                                2-butene         2,3-butanediol                                            7   2-Methyl-1-                                                                             RT,  3 h                                                                               1,2-Epoxy-2-                                                                              55%                                                hexane           methylhexane                                              8   1-Octene RT,  3 h                                                                               1,2-Octanediol                                                                            70%                                            9   trans-4-Octene                                                                          RT,  2 h                                                                               4,5-Epoxyoctane                                                                           100%                                          10   1-Decene RT,  3 h                                                                               1,2-Epoxydecane                                                                           60%                                           11   Cyclohexene                                                                             RT,  1 h                                                                               Cyclohexane-1,2-                                                                          98%                                                                 diol(trans-                                                                    Isomer)                                                  12   1-Methyl-1-                                                                             RT,  2 h                                                                               1,2-Dihydroxy-1-                                                                          70%                                                cyclohexene      methyl-cyclohexane                                       13   Cycloheptene                                                                            RT,  1 h                                                                               Epoxycycloheptane                                                                         80%                                           14   Cyclooctene                                                                             RT,  1 h                                                                               Epoxycyclooctane                                                                          80%                                           15   cis,cis-1,5-                                                                            RT,  2 h                                                                               1,2,5,6-Diepoxy-                                                                          80%                                                Cyclooctadiene   cycclooctane                                             16   Cycloooctate-                                                                           RT,  2 h                                                                               1,2-Epoxy-3,5,7-                                                                          35%                                                traene           cyclooctatriene                                          17   Cyclododecene                                                                           RT,  1 h                                                                               Epoxycyclododecane                                                                        100%                                          18   1,9-Cyclohexa-                                                                          RT,  3 h                                                                               10-Epoxy-1-cyclo-                                                                         55%                                                decadiene        hexadecene                                               19   α-Pinene                                                                          -30° C.,                                                                     1 d                                                                               exo- and endo-                                                                            55%                                                                 Epoxypinane                                              20   Limonene RT,  5 h                                                                               Limonene-mono-                                                                            35%                                                                 epoxide                                                  21   Citral   RT,  1 d                                                                               2,3-Epoxycitral                                                                           28%                                           22   Squalene RT,  2 h                                                                               Dihydroxysqualene                                                                         75%                                           23   Allyl alcohol                                                                           RT,  10 h                                                                              2,3-Epoxy-1-                                                                              90%                                                                 propanol                                                 24   2-Bromo-2-                                                                              RT,  2 h                                                                               2,3-Epoxy-2-                                                                              45%                                                butene           bromobutane                                              25   Diethyl  RT,  1 d                                                                               Diethyl epoxy-                                                                            20%                                                maleate          succinate                                                26   Methyl oleate                                                                           RT,  1 d                                                                               methyl 9,10-Dihy-                                                                         92%                                                                 droxyoctadecanoate                                       27   Methyl   RT,  2 h                                                                               Methyl 6,7-Epoxy-                                                                         80%                                                linoleate        linoleate                                                28   1,4-Naphtho-                                                                            70° C.,                                                                      18 h                                                                              2,3-Epoxy-1,4-                                                                            64%                                                quinone          naphthoquinone                                           29   3-Methyl-1,2-                                                                           RT,  1 h                                                                               3-Hydroxy-3-methyl-                                                                       45%                                                butadiene        2-butanone                                               30   3-Hexyne RT,  1 h                                                                               4-Hexen-3-one                                                                             40%                                           31   Diphenyl-                                                                               65° C.,                                                                      1 d                                                                               Benzil     71%                                                acetylene                                                                 32   Styrene  RT,  2 h                                                                               Phenylacetaldehyde                                                                        12%                                                                 (±)-Phenylethylene                                                          glycol     11%                                                                 Benzaldehyde                                                                              25%                                             33(a)                                                                             cis-Stilbene-                                                                           70° C.,                                                                      2 h                                                                               Benzaldehyde                                                                              76%                                                (1,2-Diphenyl-   cis-Stilbeneoxide                                                                          6%                                                ethylene)                                                                    (b)                                                                              cis-Stilbene-                                                                           RT,  2 h                                                                               Benzaldehyde                                                                              49                                                 (1,2-Diphenyl-   cis-Stilbeneoxide                                                                          1%                                                ethylene)                                                                 34   2,3,4,5,6-                                                                              RT,  3 h                                                                               2,3,4,5,6-Penta-                                                                          56%                                                Pentafluoro-     fluorostyreneoxide                                            styrene                                                                   __________________________________________________________________________      *RT = Room temperature (about 28° C.), h = hour, d = day                **Yield based on converted olefin.                                       

(35)

50 mg (0.2 mmol) of methylrhenium trioxide were dissolved with stirring at -10° C. in 135 ml of oxidation solution according to B. At this temperature, 25 ml of cyclohexene (20 g, 0.24 mol) were added dropwise over a period of 3 hours. Meanwhile, the color of the solution lightened somewhat. After the cyclohexene addition had been completed, the mixture was allowed to reach room temperature. Excess hydrogen peroxide was destroyed by stirring with 2 g of commercially available MnO₂ for a period of 1 hour. The suspension was filtered off through a D3 sinter/celite, subsequently washed three times with 20 ml of tetrahydrofuran in each case and the solvent was evaporated off in the vacuum of a rotary oil pump. The tacky residue was washed five times with 50 ml of n-hexane in each case and then dried under a high vacuum. Yield: 24.1 g of colorless, pulverulent 1,2-transcyclohexanediol (85%). Catalyst/product mole ratio, 1/1000.

(36) Oxidation using a compound containing 6-valent rhenium

20 mg of solid tetramethyltetraoxodirhenium (VI) (CH₃)₄ Re₂ O₄ were added to a 5 ml portion of the "oxidation solution" initially prepared according to B) from tertbutanol and H₂ O₂. This immediately produced a yellow coloration. 0.15 ml of cyclododecene was then added. This caused slight heating of the solution. After 1 hour, the mixture was worked up as in Examples 1-34 and analyzed (GC/IR/MS). 99% pure epoxycyclododecane was obtained by this procedure.

Compounds of the formula III Examples 37-52 (37) (1-Azabicyclo[2,2,2]octane)methyl(trioxo)rhenium (VII), CH₃ ReO₃.N(C₂ H₄)₃ CH

To a solution of 70 mg (0.63 mmol) of quinuclidine [N(C₂ H₄)₃ CH] in 10 ml of tetrahydrofuran were added at 20° C. with constant stirring 160 mg (0.64 mmol) of CH₃ ReO₃. The initially colorless solution instantly turned lemon yellow when the quinuclidine was added. After one hour, the solvent was removed under reduced pressure. In this way, 210 mg (91%) of product were obtained in the form of small needle-like crystals. Recrystallization from tetrahydrofuran/n-pentane (ratio by volume 3:1) alows larger crystals to be grown. M.p. 112° C. (decomp.).

C₈ H₁₆ NO₃ Re calc.: C 26.65, H 4.44, N 3.89, (360.43) found: C 27.08, H 4.37, N 3.79.

¹⁷ O-NMR spectrum: δO=566 ppm [CH₂ Cl₂ /CDCl₃ ]. The compound is characterized by single crystal X-ray structural analysis: d(Re-O)=165-173 pm, d(Re-N)=250 pm

IR [KBr]: v(Re═O), cm⁻¹ : 925 sst.

¹ H-NMR [solvent] δ(ppm, 23° C.): 1.40 (s, 3H); 1.51 (dt, ³ J(H,H)=8.06 Hz, ³ J(H,H)=3.18 Hz, 6H); 1.81 (sept, ³ J(H,H)=3.18 Hz, 1H); 2.48 (T, ³ J(H,H)=8.06 Hz, 6H) [CDCl₃ ]

(38) (1,4-Diazabicyclo[2,2,2]octane)-N,N'-bis[methyl(trioxo)rhenium(VII)], [CH₃ ReO₃ ]₂. N(C₂ H₄)₃ N]

To a solution of 130 mg (0.52 mmol) of CH₃ ReO₃ in 10 ml of tetrahydrofuran were added 58 mg (0.52 mmol) of 1,4-diazabicyclo[2,2,2]octane. This immediately caused the solution to turn deep yellow. After 1 hour, the solvent was removed under reduced pressure and the yellow, finely crystalline product was recrystallized at -30° C. from tetrahydrofuran. The yield of analytically pure product was 160 mg (85%).

C₈ H₁₆ N₂ O₆ Re₂ calc.: C 15.73, H 2.95, N 4.59, O 15.72; (610.65) found: C 15.78, H 2.95, N 4.47, O 15.74.

IR [KBr]: v(Re═O), cm⁻¹ : 909 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 1.47 (s, 6H); 2.55 (s, 12H) [CDCl₃ ]

(39) (Aniline)methyl(trioxo)rhenium(VII), CH₃ ReO₃.NH₂ C₆ H₅

36 μl (37 mg, 0.40 mmol) of freshly distilled aniline were added to a solution of 100 mg (0.40 mmol) of CH₃ ReO₃ in 10 ml of toluene. This caused the color to change immediately to yellow. After 15 min, the solvent was removed under reduced pressure and the residue was sublimed at 40° C. (1.33×10⁻³ mbar). In this way 120 mg (88%) of product were obtained as bright yellow crystals.

C₇ H₁₀ NO₃ Re calc.: C 24.56, H 2.94, N 4.09, O 14.02, Re 54.39; (342.37) found: C 24.49, H 2.99, N 4.09, O 13.81, Re 54.62.

¹⁷ O-NMR spectrum: δO=566 ppm [CH₂ Cl₂ /CDCl₃ ].

The compound is further characterized by single crystal X-ray structural analysis: d(Re-O)=169.9 pm; d(Re-N) =246.9 pm; NH₂ . . . O hydrogen bonds are present.

IR [KBr]: v(Re═O), cm⁻¹ : 927 sst.

¹ H-NMR [solvent] δ(ppm, 23° C.): 2.57 (s, 3H); 3.62 (br, 2H); 6.67 (dd, ³ J(H,H)=7.32 Hz, ⁴ J(H,H)=1.22 Hz, 2H); 6.75 (t, ³ J(H,H)=7.32 Hz, 1H); 7.14 (m; 2H) [CDCl₃ ]

(40) (2,2'-Bipyridine)methyl(trioxo)rhenium(VII), CH₃ ReO₃.C₁₀ H₈ N₂

A slight excess (0.79 g, 4.4 mmol) of 2,2'-bipyridine is added at room temperature with constant vigorous stirring to a solution of 1.00 g (4.0 mmol) of CH₃ ReO₃ in 100 ml of toluene. A yellow precipitate was immediately formed. After a reaction time of 30 min, the precipitate was allowed to settle and the solvent was decanted off. Excess 2,2'-bipyridine was removed by washing three times with 25 ml of toluene in each case. This procedure was repeated twice using n-pentane. The solvent was finally removed under an oil pump vacuum. In this way 1.59 g (97%) of the compound were obtained analytically pure.

M.p. 138° C. (decomp.).

C₁₁ H₁₁ N₂ O₃ Re calc.: C 32.56, H 2.71, N 6.91, O 11.84; (405.43) found: C 32.68, H 2.74, N 6.80, O 12.02.

IR [KBr]: v(Re═O), cm⁻¹ : 910 sst, 940 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 1.95 (s, 3H); 7.35 (m, 2H); 7.87 (m, 2H); 8.50 (d, ³ J(H,H)=7.93 Hz, 2H); 8.66 (d, ³ J(H,H)=4.88 Hz, 2H) [CD₂ Cl₂ ]

(41) (2,2'-bipyridine)methyl(oxo)dichlororhenium(V), CH₃ ReOCl₂.C₁₀ H₈ N₂

To 0.50 g (1.23 mmol) of a suspension of the compound according to Example 30 in 30 ml of methylene chloride were added dropwise at room temperature with constant stirring 314 μl (2.44 mmol) of freshly distilled trimethylchlorosilane. Then an equimolar amount (322 mg; 1.23 mmol) of triphenylphosphane was added. The solution immediately turned deep violet in color. Then the reaction mixture was boiled under reflux until the violet color had completely disappeared and the reaction solution had become yellowish brown (reaction time about 1 hour). After cooling the solution to room temperature, the product was quantitatively precipitated by adding 60 ml of n-pentane and the solvent, which was now only faintly red in color, was decanted off. The product was purified by washing several times with 10 ml of toluene in each case. Recrytstallization from methylene chloride at -30° C. allowed small, cubic crystals to be grown. The compound was obtained in 98% yield (0.54 g).

C₁₁ Cl₂ H₁₁ N₂ ORe (444.33): calc.: C 29.73, H 2.50, N 6.30, O 3.60, Cl 15.96; found: C 29.64, H 2.51, N 6.20, O 3.63, Cl 16.01.

IR [KBr]: v(Re═O), cm⁻¹ : 988 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 5.41 (s,3H); 7.09 (m, 1H); 7.46 (m, 1H); 7.63 (m, 1H); 7.90 (m, 1H); 8.00 (m, 2H); 8 36 (m, 1H); 8.47 (m, 1H) [CD₂ Cl₂ ]

(42) (2,2'-Bipyridine)methyl(oxo)bis(trimethylsilylmethyl)rhenium(V), CH₃ ReO[CH₂ Si(CH₃)₃ ]₂.C₁₀ H₈ N₂

A solution of 1.0 ml of (trimethylsilyl)methylmagnesium chloride, (CH₃)₃ SiCH₂ MgCl (1.0 molar solution in diethyl ether; 1.0 mmol), was diluted with 10 ml of toluene and then cooled to -78° C. and finally to this solution a suspension, likewise at -78° C., of 175 mg (0.39 mmol) of the compound according to Example 41 in 20 ml of toluene was added. The reaction mixture was then brought to room temperature in the course of 2 hours. Above about -30° C., a slight greenish coloration was observed; finally, a bluish green solution was obtained. After the solution had reached room temperature, it was stirred for 1 hour and finally the solvent was removed under an oil pump vacuum. The residue was introduced into a chromatography column and subjected to chromatography at 10° C. on silica gel (supplied by Merck; kieselgel 60, particle size 0.063-0.200 mm). The product was eluted as the deep-green zone with n-pentane/toluene (ratio by volume 1:1). This solvent mixture is suitable for growing single crystals. The eluate was subjected to evaporation in an oil pump vacuum to obtain 60 mg (28%) of compound which was insensitive to air and water.

C₁₉ H₃₃ N₂ OReSi₂ calc.: C 41.65, H 6.07, N 5.11; (547.86) found: C 41.72, H 6.36, N 4.42.

IR (KBr): v(Re═O), cm⁻¹ : 975 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 0.34 (s, 18H); 2.22 (d, ² J(H,H)=10.98 Hz , 2H); 3.15 (d, ² J(H,H)=10.98 Hz, 2H); 3.67 (s, 3H); 5.89, 6.26, 6.35, 6.58, 6.69, 7.19, 7.71, 8.72 (m, 8H) [d⁸ -toluene]

(43) (2,2'-Bipyridine)trimethyl(oxo)rhenium, (CH₃)₃ ReO.C₁₀ H₈ N₂

To a suspension of 888 mg (2.0 mmol) of the compound according to Example 41 in 60 ml of toluene were added dropwise at -78° C. with constant stirring 2.69 ml of methyllithium (1.6 molar solution in diethyl ether; 4.3 mmol). The reaction solution was stirred at this temperature for about 30 min and then brought to room temperature over a period of 3 hours. A reaction was already brought about at a temperature of -65° C. (green coloration of the reaction mixture). After 3 hours, the deep green colored solution had reached room temperature and depositing of a fine precipitate of LiCl was observed. The solvent was then removed under reduced pressure and the dark, almost black residue was extracted by being taken up in toluene. The deep green solution was filtered through ®Celite to remove completely the precipitated LiCl and the solvent was then evaporated off under reduced pressure. 726 mg (90%) of compound were obtained as an almost black powder which was stable in air and which dissolved in n-pentane and toluene giving a deep green color, in diethyl ether, tetrahydrofuran and acetone giving a deep blue color, and in methylene chloride and chloroform giving a turquoise color.

C₁₃ H₁₇ N₂ ORe calc.: C 38.67, H 4.24, N 6.94, O 3.97. (403.40) found: C 38.70, H 4.10, N 6.79, O 4.00.

IR [KBr]: v(Re═O), cm⁻¹ : 976 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 2.40 (s,6H); 3.47 (s, 3H); 6.84, 7.19, 7.57, 7.86, 7.91, 8.28, 8.79, (m, 8H) [CDCl₃ ]

(44-46) Isomers of(methoxyaniline)methyl(trioxo)rhenium(VII), CH₃ ReO₃.CH₃ OC₈ H₄ NH₂

To a solution of 80 mg (0.32 mmol) of CH₃ ReO₃ in 10 ml of toluene were added 40 mg (0.33 mmol) of the corresponding substituted aniline derivative, the solution immediately turning yellow. After 30 min. the volume of solvent was reduced to half using an oil pump vacuum. Then 10 ml of n-hexane were added. In each case, the produce (Examples 44-46) crystallized out at -35° C. and was then dried over a high vacuum.

(44) 2-Methoxyaniline compound: yellow crystals; yield 110 mg (92%)

C₈ H₁₂ NO₄ Re calc.: C 25.80, H 3.25, N 3.76; (372.40) found: C 25.75, H 3.15, N 3.76.

IR [KBr]: v(Re═O), cm⁻¹ : 929 sst

¹ H-NMR [solvent] δ(ppm, 23° C.): 2.58 (s, 3H); 2.90 (br, 2H); 3.83 (s, 3H); 6.77 (m, 4H) [CDCl₃ ]

(45) 3-Methoxyaniline compound: yellowish brown crystals; yield 110 mg (92%).

C₈ H₁₂ NO₄ Re calc.: C 25.80, H 3.25, N 3.76; (372.40) found: C 25.73, H 3.23, N 3.77.

IR [KBr]: v(Re═O), cm⁻¹ : 915 sst, 944 st, 962 st

¹ H-NMR [solvent] δ(ppm, 23° C.): 2.59 (s, 3H); 3.75 (s, br, 5H); 6.23 (t, ⁴ J(H,H)=2.44 Hz, 1H); 6.27 (dt, ³ J(H,H)=7.93 Hz, ⁴ J(H,H)=1.22 Hz, 1H); 6.31 (dd, ³ J(H,H)=9.16 Hz, ⁴ J(H,H)=2.44 Hz, 1H); 7.04(t, ³ J(H,H)=7.93 Hz) [CDCl₃ ]

(46) 4-Methoxyaniline compound: reddish brown crystals; yield 110 mg (92%).

C₈ H₁₂ NO₄ Re calc.: C 25.80, H 3.25, N 3.76. (372.40) found: C 25.93, H 3.12, N 3.72.

IR [KBr]: v(Re═O), cm⁻¹ : 909 sst, 934 sst, 962 st

¹ -NMR [solvent] δ(ppm, 23° C.): 2.56 (s, 3H); 3.39 (br, 2H); 3.73 (s, 3H); 6.63 (d, ³ J(H,H)=9.16 Hz, 2H); 6.73 (d, ³ J(H,H)=8.13 Hz, 2H) [CDCl₃ ]

(47) [2-(Aminomethyl)pyridine]methyl(trioxo)rhenium(VII), CH₃ ReO₃.NC₅ H₄ CH₂ NH₂

33 μl (35 mg, 0.32 mmol) of 2-(aminomethyl)pyridine were added to a solution of 80 mg (0.32 mmol) of CH₃ ReO₃ in 10 ml of toluene. A yellow precipitate was immediately formed from which the supernatant was decanted, and then the solid was washed twice with 10 ml of toluene in each case and finally dried under an oil pump vacuum. In this way 110 mg (quantitatively) of yellow product were obtained.

C₇ H₁₁ N₂ O₃ Re calc.: C 23.53, H 3.10, N 7.84, O 13.43, Re 52.10; (357.38) found: C 23.73, H 3.08, N 7.78, O 13.70, Re 52.05.

IR [KBr]: v(Re═O) cm⁻¹ : 908 sst, 935 sst

¹ H-NMR [solvent] δ(ppm, 23° C: 2.12 (s, 3H); 3.53 (br, 2H); 5.04 (d, ² J(H,H)=22.0 Hz, 1H); 6.09 (d, ² J(H,H)=22.0 Hz, 1H); 8.19 (m, 1H); 8.30 (m, 1H); 8.83 (m, 1H); 9.23 (m, 1H) [CD₃ CN]

(48) [N-(2-Aminoethyl)pyrrolidine]methyl(trioxo)rhenium(VII), CH₃ ReO₃.(C₄ H₈ N--CH₂ CH₂ NH₂)

41 μl (37 mg, 0.32 mmol) of N-(2-aminoethyl)pyrrolidine were added to a solution of 80 mg of CH₃ ReO₃ (0.32 mmol) in 10 ml of toluene. A yellow coloration was immediately produced. After about 30 sec., a yellow precipitate formed. The supernatant was decanted off; the solid was then washed with 10 ml of toluene and the solvent removed under an oil pump vacuum. 100 mg (85%) of compound were obtained as a yellow powder.

C₇ H₁₇ N₂ O₃ Re calc. C. 23.13, H 4.72, N 7.71. (363.43) found: C 23.31, H 4.64, N 7.61.

(9) [(N,N-dimethylamino)acetonitrile]methyl(trioxo)rhenium(VII), CH₃ ReO₃.[(CH₃)₂ NCH₂ CN]

24 mg (27 μl, 0.28 mmol) of (N,N-dimethylamino)acetonitrile were added to a solution of 70 mg (0.28 mmol) of CH₃ ReO₃ in a mixture of 5 ml of toluene and 5 ml of n-pentane. When the light yellow colored solution was cooled to -35° C., 80 mg (86%) of yellowish translucent crystals were formed in the course of 20-30 h and these were dried under an oil pump vacuum.

C₅ H₁₁ N₂ O₃ Re calc.: C 18.02, H 3.33, N 8.40; (333.36) found: C 17.91, H 3.28, N 8.04.

(50) [(N,N-Dimethylamino)acetone]methyl(trioxo)rhenium(VII), CH₃ ReO₃.[(CH₃)₂ NCH₂ C(O)CH₂ ]

To a solution of 70 mg (0.28 mmol) of CH₃ ReO₃ in 10 ml of n-pentane were added 28 mg (32 μl, 0.28 mmol) of (N,N-dimethylamino)acetone. The initially colorless solution immediately turned yellow. The solution was then left to crystallize at -35° C. for 10-30 h. 80 mg (82%) of compound were obtained in the form of yellow platelets.

C₈ H₁₄ NO₄ Re calc.: C 20.57, H 4.03, N 4.00; (350.39) found: C 20.84, H 4.02, N 3.99.

(51) Methyl(pyridine-N-oxide)trioxorhenium(VII), CH₃ ReO₃.ONC₅ H₅

70 mg (0.28 mmol) of CH₃ ReO₃ and 60 mg (0.64 mmol) of pyridine-N-oxide were mixed in 10 ml of toluene. A colorless solution was formed. This was kept at -35° C. After 10 to 30 hours, the compound crystallized in the form of yellow needles. The product was dried under a high vacuum.

Yield: 80 mg (80%).

C₆ H₈ NO₄ Re calc.: C 20.93, H 2.34, N 4.07; (344.34) found: C 21.12, H 2.45, N 4.07.

(52) Methyl[tricarbonyl(η⁵ -pyrrolyl)manganese]trioxorhenium(VII), CH₃ ReO₃.[(η⁵ -C₄ H₄ N)]Mn(CO)₃

To a solution of 70 mg (0.34 mmol) of tricarbonyl(η⁵ -pyrrolyl)manganese, (η⁵ -C₄ H₄ N)Mn(CO)₃, in 10 ml of diethyl ether, were added 85 mg (0.34 mmol) of CH₃ ReO₃. After 20 hours' stirring at room temperature, the mixture was filtered. 10 ml of n-hexane was added to the filtrate and the solution was allowed to crystallize at -35° C. for 10-30 hours. Yield: 110 mg (71%); yellowish brown crystals.

C₆ H₇ MnNO₈ Re calc.: C 21.15, H 1.55, Mn 12.00, N 3.08; (454.29) found: C 21.27, H 1.59, Mn 12.09, N 3.10.

Examples 53-56 Oxidation using compounds III

To 2.68 ml of the oxidation solution initially obtained according to B were added 20 mg of CH₃ ReO₃.L. Meanwhile, an immediate yellow coloration was observed. To the catalyst solution prepared in this way was added 0.5 ml of cyclohexene. In the course of 3 h the yellow coloration disappeared and the reactant/product ratio which had been reached remained constant. The mixture was subsequently worked up as indicated in Examples 1 to 34. The results can be seen in Table 2 below.

                  TABLE 2                                                          ______________________________________                                         Exam-             Reaction                                                     ple   Ligand L    conditions                                                                               Products   Yield                                   ______________________________________                                         53    m-Anisidine RT, 20 h  1,2-cyclohexane-                                                                          50%                                                                 diol                                               54    p-Anisidine RT, 20 h  1,2-cyclohexane-                                                                          55%                                                                 diol                                               55    Methyl-     RT, 20 h  Epoxycyclo-                                                                               75%                                           ephedrine             hexane                                             56    Dimethylamino-                                                                             RT, 20 h  1,2-cyclohexane-                                                                          51%                                           acetonitrile          diol                                               ______________________________________                                          *RT = room temperature (about 28° C.)                             

Examples 57-63 Oxidation catalyst fixed on a polymer

To a suspension of 9.20 g of poly(4-vinylpyridine) (commercial product "Reilllex" supplied by Aldrich Chemie GmbH, Steinheim/Albuch, catalog No. 22,696-3) in 200 ml of tetrahydrofuran was added 0.80 g (3.2 mmol) of CH₃ ReO₃ and the mixture was thoroughly stirred for 20 hours using a magnetic stirrer. During this period, the polymer changed from colorless to bright yellow with the formation of a complex of CH₃ ReO₃. The solvent was then decanted off. The residue was washed five times with 20 ml of tetrahydrofuran each time and finally dried under an oil pump vacuum. A yellow powder remained. The results of the elemental analysis (Re calculated 6.0, found 6.1%) showed that the CH₃ ReO₃ had become bound to the polymer substrate without losses. This measure greatly reduced the volatility of CH₃ ReO₃ : the compound could no longer be removed from the substrate at temperatures up to 150° C. even under a high vacuum.

Similar catalysts in which CH₃ ReO₃ had been taken up on polymers were obtained by the same procedure using

    ______________________________________                                         58)    Poly(2-vinylpyridine)                                                                           (Aldrich No. 18,950-2)                                 59)    Poly(2-vinylpyridine-co-                                                                        (Aldrich No. 18,127-7)                                        styrene)                                                                60)    Poly(acrylamide) (Aldrich No. 19,207-4)                                 61)    Poly(vinylpyrrolidone)                                                                          (Aldrich No. 85,648-7)                                 62)    Polyimide        (Aldrich No. 18,464-0)                                 63)    Nylon 6          (Aldrich No. 18,111-0)                                 ______________________________________                                    

Examples 64-66 Oxidation using methylrhenium trioxide fixed to a polymer

To 3 ml of the oxidation solution initially obtained according to B were added 20 mg of the catalyst according to Example 57. The insoluble, catalyst-containing polymer immediately turned yellow in color. To the suspension was added with stirring the olefin to be oxidized, during which heating was observed. After 1 hour, the yellow coloration of the polymer had disappeared and the reactant/product ratio which had been reached remained constant even after a relatively long waiting period. After a further 30 min, the catalyst was filtered off on a glass sinter and washed three times with 20 ml of tetrahydrofuran each time. After drying under an oil pump vacuum, the catalyst can be used for further oxidation batches. The filtrate was worked up as described in Examples 1-34. The results are summarized in Table 3.

                  TABLE 3                                                          ______________________________________                                         Exam-            Reaction                                                      ple   olefin     conditions*                                                                              Products    Yield                                   ______________________________________                                         64    Cyclohexene                                                                               RT, 20 h  epoxycyclo- 27%                                                                hexane                                              65    Methyl oleate                                                                             RT, 20 h  methyl 9,10-epoxy-                                                                         85%                                                                octadecanoate                                       66    Allyl alcohol                                                                             RT, 20 h  1,2-epoxypropane-                                                                          20%                                                                3-ol                                                ______________________________________                                          *RT = room temperature (about 28° C.)                              

We claim:
 1. A compound of the general formula

    (R.sup.11 Re).sub.k O.sub.l R.sup.12.sub.m. L.sub. n       (III),

wherein R¹¹ is a non-aromatic hydrocarbon group of 1 to 10 carbon atoms or aralkyl of 7 to 9 carbon atoms, each being bound to rhenium by a carbon atom bearing at least one hydrogen atom, R¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain up to 3 silicium bridging atoms, or is a phenyl group which is unsubstituted or contains up to 3 substituents selected from the group consisting of alkyl, alkoxy and combinations thereof, said substituents containing at most 6 carbon atoms or containing up to 5 fluorine atoms, L is a ligand which is bound to the rhenium via 1 to 3 atoms of at least one element selected from the group consisting of oxygen and nitrogen, and in which the indices k is 1 or 2, l is an integer from 1 to 3·k, m is zero or an integer from 1 to 2·k and n is an integer from 1 to 3 k and the indices k, l, m and n are selected such that their combination conforms to the 5- to 7-valency of rhenium.
 2. A compound of the formula

    (polymer).sub.f.(CH.sub.3 ReO.sub.3).sub.g                 (VI)

in which the CH₃ ReO₃ 3Re03 is bound to the polymer via amino nitrogen or amido nitrogen of the polymer and in which the quotient g/f represents the ratio by weight of the two components and is in the range of from 0.01 to 0.2.
 3. A compound as claimed in claim 2, wherein the quotient g/f is in the range of from 0.02 to 0.1.
 4. A catalyst for the oxidant of C--C-multiple bonds comprising at least one compound selected from the group consisting ofa) a compound of the formula

    (R.sup.11 Re).sub.k O.sub.l R.sup.12.sub.m.L.sub.n         (III),

whereinR¹¹ is a non-aromatic hydrocarbon group of 1 to 10 carbon atoms or aralkyl of 7 to 9 carbon atoms, each being bound to rhenium by a carbon atom bearing at least one hydrogen atom, R¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain up to 3 silicium bridging atoms, or is a phenyl group which is unsubstituted or contains up to 3 substituents selected from the group consisting of alkyl, alkoxy and combinations thereof, said substituents containing at most 6 carbon atoms or containing up to 5 fluorine atoms, L is a ligand which is bound to the rhenium via 1 to 3 atoms of at least one element selected from the group consisting of oxygen and nitrogen, and in which the indices k is 1 or 2, l is an integer from 1 to 3·k, m is zero or an integer form 1 to 2·k and n is an integer from 1 to 3·k and the indices k, l, m and n are selected such that their combination conforms to the 5- to 7-valency of rhenium, and b) a compound of the formula

    (polymer).sub.f.(CH.sub.3 ReO.sub.3).sub.g                 (VI)

in which the CH₃ ReO₃ is bound to the polymer via amino nitrogen or amido nitrogen of the polymer and in which the quotient g/f represents the ratio by weight of the two components and is in the range of from 0.01 to 0.2.
 5. A compound as claimed in claim 1, wherein the general formula (III)R¹¹ is an alkyl radical having 1 to 10 carbon atoms or an cycloalkyl radical having 5 to 10 carbon atoms, R¹² is a linear or branched aliphatic hydrocarbon radical having 1 to 10 carbon atoms, and L is a member of the group consisting of an amine, an aliphatic azacycle, an aromatic azacycle, a O,O'-, N,O- and N,N'-chelate ligand, a substituted piperazine, an aminosubstituted piperidine, an aminosubstituted pyrrolidine, a methoxysubstituted pryidine, a 1,3-diketone, a 1,2-diketone, a β-aminoalcohol, a β-aminoaldehyde, a β-aminoketone, a 1,2-diimide, a β-aminoether, an aromatic N-oxide, a 1,2-diamine and a hydroxycarboxylic acid.
 6. A compound as claimed in claim 1, wherein R¹¹ is methyl, the index k is 1, the index l is 3 and the index m is zero.
 7. A compound as claimed in claim 2, wherein the polymer is poly(4-vinylpyridine), poly(2-vinylpyridine), poly(2-vinylpyridine-co-styrene), poly(acrylamide), poly(vinylpyrrolidone), polyimide or nylon
 6. 8. A compound as claimed in claim 1 which is a member of the group consisting of CH₃ ReO₃.N(C₂ H₄)₃ CH, (CH₃ ReO₃).(N(C₂ H₄)₃ N), CH₃ ReO₃.NH₂ C₆ H₅, CH₃ ReO₃.C₁₀ H₈ N₂, CH₃ ReOCl₂.C₁₀ H₈ N₂, CH₃ ReO(CH₂ Si (CH₃)₃)₂.C₁₀ H₈ N₂, (CH₃)₃ ReO.C₁₀ H₈ N₂, CH₃ ReO₃.CH₃ OC₆ H₄ NH₂, CH₃ ReO₃. NC₅ H₄ CH₂ NH₂, CH₃ ReO₃ (C₄ H₈ N.CH₂ CH₂ NH₂), CH₃ ReO₃.((CH₃)₂ NCH₂ CN), CH₃ ReO₃.((CH₃)₂ NCH₂ C(O)CH₃), CH₃ ReO₃.ONC₅ H₅ and CH₃ ReO₃. ((n⁵ -C₄ H₄ N))Mn(CO⁻)₃. 